Linear condensation polymers of a polymethylene glycol and a diaminodiphenyl



UnitedStates Patent LINEAR CONDENSATION POLYMERS OF A POLY- METHYLENE GLYCOL AND A DIAMINODI- PHENYL I Marion R. Lytton, West Chester, Pa., assignorto American Viscose Corporation, Philadelphia, Pa., a corporation of Delaware No Drawing. Application March 4, 1952, Serial No. 274,825

19 Claims. (Cl. 202) Patented Oct. 25, 1955 where x is an integer from 6 to 18 and n is an integer greater than one and the several substituents R1, R2, R3, R4, R5, and R6 are each separately selected from the group consisting of hydrogen, halogen, alkyl radicals having 1 to 3 carbon atoms, and aryl radicals of the benzene series; the aforesaid substituents on each nucleus of the bracketed unit may be the same or different, and the substituents on one nucleus of the bracketed unit may be the same as or different from those on the other nucleus of the unit. These products are poly[(2,2-diamino)diphenylene alkanes(5,5)] and poly[(3,3-diamino)diphenylene alkanes(6,6')]. Thus, the polymeric condensation product of the 2,2-diaminodiphenyl and hexamethylene glycol may be designated as poly[(2,2'-diamino)diphen- This invention relates to polymeric materials. More ylene(1,6-)hexane(5,5) and the condensate from the particularly it relates to synthetic linear condensation 2,2'-diaminodiphenyl and decamethylene glycol may be polymers and molded and extruded articles comprising designated as poly[(2,2-diamino)diphenylene (1,10-)- them. decane(5,5')]. The condensates may also be generically In accordance with the invention it has been found designated as poly-[bis-(p-aminophenyl)-alkanes] or polythat a new class of extremely tough condensation poly- 20 Ealpha,omega-(-di-p-aminophenyl) alkanes]. mers having film-forming and other valuable character- The repeating structural units of the polymeric condenistics are obtained by heating a bifunctionally reactive sates produced from 2,2'- or 3,3-diaminodiphenyls having alcohol with diaminodipbenyls unsubstituted in the posialkyl, aryl or halogen nuclear substituents are the same tions para to the amino groups, or their alkyl, aryl or as in the formulae (a) and (b) except for the presence halogen nuclearly substituted derivatives. of such substituents on the phenyl rings. In the substi- The diaminodiphenyls which may be used as starting tuted products each phenyl ring of each unit of the polymaterials are 2,2-diaminodiphenyl, 3,3'-diaminodiphenyl, meric condensate may carry from 1 to 3 nuclear substitand their nuclearly substituted derivatives having alkyl uents of the classes stated. The substituents on one phenyl radicals containing from 1 to 3 carbon atoms, aryl radiring of the unit may be the same as or different from subcals of the benzene series, or halogen atoms attached distituents on the remaining ring of the unit. The presence rectly to one or both of the phenyl rings in any position of the substituents mentioned does not interfere with the other than para to the amino groups. condensation reaction or inhibit rearrangement of the The dihydric alcohols which may be used are those intermediate di-iminodiphenyl alkane to the final polyglycols which do not tend to undergo intramole'cula'r reacmeric product. tion with ring formation, i. .e., polymethylene glycols in For highest yields the diaminodiphenyl and glycol are which the terminal hydroxyl groups are separated by a used in equimolecular proportions. The diaminodiphenyl chain of at least six, preferably six to eighteen, methylene may be partly replaced by its dihydrochloride or dihydrogroups. bromide. In the preferred embodiment, the diaminodi- It is believed that when the diaminodiphenyl and glycol phenyl and glycol are used in equimolecular proportions are heated, the hydroxyl groups of the glycol combine and, in addition, the reaction mixture initially comprises with a hydrogen atom on each of the amino groups wherethe dihydrochloride or dihydrobromide of the diaminoby water is split out with the production of an interdiphenyl in an amount up to about one-half by weight mediate heat-labile di-iminodiphenyl in which the imino of the diaminodiphenyl. groups are linked together by the alkane nucleus derived It is desirable to remove the by-product water as the from the glycol. On continued heating, this intermediate heating proceeds in order to expedite the condensation rearranges, the amino groups being restored and the aland production of the poly-(diaminodiphenylene alkane). kane nucleus shifting to link the two phenyl radicals of One means of accomplishing this objective is to conduct each unit of the polymer at their positions para to the the reaction in the presence of a dehydrating agent such amino groups. as zinc chloride or cobalt chloride. If this is done, the

The polymeric linear condensates may be designated zinc chloride or cobalt chloride double compound formed as poly-(diaminodiphenylene-alkanes) and are built up can be decomposed after completion of the condensation from repeating structural units as shown in brackets in by boiling the crude condensation mixture with an excess the formulae ((1) and (b) below, the unit in (a) being (e. g., 3 to 10 times the weight of the mixture) of aqueous repeated in the product obtained from 2,2-diaminodialkali metal hydroxide as a concentrated (15-30%) soluphenyl (or derivatives thereofland the glycol, the unit tion. in (1)) being repeated in the product from 2,3-diamino- The poly-(diaminodiphenylene alkanes) are somewhat diphenyl (or derivatives thereof) and the glycol: tacky, unusually tough products which are fusible at tem- (a) 1?; NH: ITIH: Ilu R1 IIIHi I|\TH: Ru

R R5 R R5 R0 R4 I a 15th (CH2):-

(b) NH: R1 R0 17TH: IITH: R1 Re NH:

R R; R Rt Ra R4 R3 R4 -(C H2) (CH2) 4:

peratures between 50 C. and 55 C., and soluble in acetone and benzene.

Furthermore, N-acylation products of the polymers, such as poly-(N,N-diacyl-diaminodiphenylene alkanes) fillers, plasticizers, mold lubricants, special effect materials, etc.

Fillers which may be present in molding compositions comprising the polymers include alpha-cellulose, wood may be obtained by heating the unacylated polymeric 5 flour, walnut shell flour, asbestos in the form of a powder condensates with the anhydride of a lower fatty acid conor long or short fibers, finely divided silicon carbide, cartaining 2 to 4 carbon atoms. In general, the acylated bon black, diatomaceous earth, slate dust, powdered rutile, polymers are characterized by higher fusing or melting powdered or flake mica, powdered quartz, fibers and cloth temperatures than the parent polymeric condensates. cuttings (e. g., fibers or cloth cuttings of silk, rayon, wool, Thus, the N,N-diacetyl derivative of poly[(2,2'-diamilinen, cotton, nylon, glass or polymeric or copolymeric' no)diphenylene(1,10-)decane(5,5)] fuses between 65 acrylonitrile), ground cork, sand, etc. C. and 70 C. while the N,N-diacetyl derivative of Useful plasticizing agents include dialkyl phthalates poly[(2,2-diamino)diphenylene(1,6-)hexane(5,5)l fuses such as dibutyl and dioctyl phthalates. between 75 C. and 80 C. The acetylated polymeric As mold lubricants there may be used zinc stearate, condensates also differ from the parent polymeric macalcium stearate, mixtures thereof, or natural or synterials in being hard, brittle, and non-tacky. The N,N'- thetic waxes. diacyl derivatives obtained by reacting the po1y[(2,2'- These molding adjuvants and other plastic materials, diamino)diphenylene alkanes(5,5)] and poly[(3,3-diaif such are used, may be mixed with the finely divided mino)diphenylene alkanes(6,6')] with the lower fatty poly-(diaminodiphenylene alkanes) in a Banbury mixer acid anhydride are made up, respectively, of repeating or on conventional milling rolls, and the compositions structural units shown in brackets in the formulae as may be molded with or without preliminary shaping therefolloWs: of to convenient pellet form.

I I I l I R: R4 a R4 ITTHIV/R lit; ITIHR' IYHR' R1 Rs NHR' |n where x is from 6 to 18, n is greater than one, the sub- Examples of the nuclearly substituted 2,2- and 3,3- stituents R1, R2, R3, R4, R5, and Rs are as defined herediaminodiphenyls which may be condensed with the glycol inabove and R is the acyl radical having 2 to 4 carbon or amixture of the glycols include:

atoms. I I

The poly-(diaminodiphenylene alkanes) and their ace- 32233332:g gigzgg gigiigz i tyl denvatiyes can be formed into synthetic fibers for use 22, diamino 44 dichlorodiphenyl in applications where comparat vely low softening and z zgdi i s h 1di 1 melting temperatures are not a d1sadvantage, for example 3,3'gdiaminoa2, dipropyldipheny1 1n the production of felt-like fibrous articles comprlsmg 3 5, dibromodipheny1 autogenously bonded fibers. The polymers may also be 3,3I diamin0 22/ diphenyldiPheny1 used in the production of films, coatings, sealants, ad- Th f 11 1 h th b hesives, for laminating similar and dissimilar surfaces, and e o owmg exam? es m l m e Parts glyen are y for the production of molded massive articles of diunless otherwlse Speclfied are lllustratlve of the verse size and cross-section, either alone or in admixture Invention with other plastic, moldable materials and/or molding Example I adjuvants. They can be melt-extruded as such or in mix- 52.2 parts of decamethylene glycol, 55.2 parts of 2,2- tures with plasticizing and/or other extrudable plastics to diaminodiphenyl, 25.8 parts of the dihydrochloride of form films, tapes, tubes, ribbons, rods or other shaped 2,2-diaminodiphenyl and 49.2 parts of zinc chloride were articles. Thus, they may be heated to their fusing temmechanically mixed in a reaction vessel and heated to perature to obtain a hot melt which can be extruded under 59 165 over a period of six hours. The mixture was then pressure to deposit a film on a surface from which it can heated at 165 C. for 15 hours and finally at between be stripped off or on a suitable substrate to which it 240 C. and 255 C. for eight hours, the mass being can be adhered with the aid of pressure. For instance, intermittently homogenized by stirring during the first the polymeric condensates may be melted in a heated part of the heating. The mass was allowed to cool, and cylinder or the like and pumped through a film-forming 60 then boiled three successive times with 250 parts of an extrusion die, or they may be fed into a conventional aqueous 18% sodium hydroxide solution. Between each screw mixer-extruder and extruded as a cylindrical rod boiling, the zinc salts were decanted 01f. On final boiling which is broken into small pieces and then fed into a no further zinc salts appeared. screw extruder in which it is melted and forced through The polymer was washed free of caustic and steaman extrusion die. distilled to remove low molecular weight fractions and Also, the poly-(diaminodiphenylene alkanes) and the other impurities. The non-volatile polymer was dried in a v ted products thereof may be dissolved in a suitable a vacuum over concentrated H2SO4. The poly[(2,2'-disolvent such as acetone or benzene and cast to films amino)diphenylene(1,10-)decane(5,5'l] thus obtained which may be self-supporting or adhered to a substrate was a very tough, somewhat tacky product which could such as a regenerated cellulose film. Or the solutions may 79 be cut with a sharp knife and melted at 50 to 55 C. It be used in coating paper, textiles, and other materials. was soluble in acetone and benzene.

The poly-(diaminodiphenylene alkanes) and the cor- About 5.4 parts of the polymer were dissolved in about responding acetylated polymers may be molded by com- 100% of its weight of acetic anhydride, and the solution pression or injection molding techniques and for this purwas warmed on a steam bath for two hours. It was pose they may be mixed with other thermoplastic resins, cooled, filtered, and the excess acetic anhydride in the '5 filtrate was decomposed by boiling in distilled-water. The acetylated polymer was precipitated, washed, and dried. It was hard, brittle and non-tacky, soluble in benzene, acetone, glacial acetic acid, ethanol and ether, insoluble in water and methanol, and melted at 65 to 70 C.

Example 11 A portion of the acetylated polymeric condensate of Example I was dissolved in benzene to obtain a .15 solution which was cast onto a heated surface to form a pliable, tough film which could be readily stripped 01f the casting surface without tearing orcrumbling.

Example III About 35.4 parts of hexamethylene glycol, 55.2 parts of 2,2-diamindiphenyl, 25.8 parts of the dihydrochloride of 2,2-diaminophenyl, and 49.2 parts of zinc chloride were well mixed in a vessel and heated to 160 C. over a period of eight hours. The mixture was then heated for two hours at 200 C., and finally for 15 hours at between 230 C. and 250 C. During the initial heating period, the reaction mixture was homogenized intermittently by stirring. The mass was cooled and the zinc salts were decomposed and removed as in Example I, after which the residue was washed and steam-distilled. Yield: 72 parts of poly (2,2-diamino) diphenylene( 1.6-)hexane- (5,5)]. The dried polymer was slightly tacky and extremely tough and diflicult to cut or break. It was soluble in acetone and benzene, and melted between 50 C. and 55 C.

Example IV About parts of the polymer of Example III were dissolved in 81.2 parts of acetic anhydride. The solution was cooled, poured into water, boiled, and again cooled. The solid acetylated polymer was filtered ofi, washed and dried. Yield, 8.0 parts. It was a hard solid having a melting point between 75 C. and 80 C. The acetylated polymer was soluble in acetone, glacial acetic acid, ethanol and ether, insoluble in water and methanol.

Benzene and acetone solutions of the acetylated polymeric condensate were cast to tough flexible films.

The decamethylene and hexamethylene glycols used in Examples I and III could be replaced by other glycols containing up to eighteen methylene groups in a chain separating the terminal hydroxyl groups, and the diaminodiphenyls could be replaced by the nuclearly substituted derivatives previously mentioned. Lower temperatures than those stated in the examples might be used but require longer heating times and therefore it is preferred to heat the mixed reactants to about 160 C. to 165 C. until the condensation is initiated, and then elevate the temperature to between 200 and 250 C. until polymerization is complete.

As various other changes and modifications may be made in practicing the invention without departing from its spirit and scope, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

I claim:

and N-acylation products of the compounds of (a) and (b) in which each acyl group has from 2 to 4 carbon atoms; in each of formulae (:1) and (b), 1: being an integer from 6 to 18, n being an integer greater than one, and the several substituents R1, R2, R3, R4, R5, and Re each having separately selected from the class consisting of hydrogen, halogen, alkyl radicals having 1 to 3 carbon atoms, and aryl radicals of the benzene series.

2. A composition of matter comprising a polymeric substance defined in claim 1 dissolved in a solvent therefor.

3. A poly[(2,2' diamino)diphenylene(l,6 )hexane ')l- 4. A composition of matter comprising a polymeric substance defined in claim 3 dissolved in a solvent therefor.

5. A poly[(2,2 diamino)diphenylene(l,l0 )decane (5,5')].

6. A composition of matter comprising a polymeric substance defined in claim 5 dissolved in a solvent therefor.

7. An N-acylation product of a polymeric substance defined in claim 6, the acyl groups having 2 to 4 carbor atoms.

8. A composition of matter comprising a product defined in claim 7 dissolved in a solvent therefor.

9. The N,N'-diacetyl derivative of poly[ (2,2-diamino) diphenylene( l,10-)decane(5 ,5 l

10. A composition of matter comprising a product defined in claim 9 dissolved in a solvent therefor.

11. The N,N-diacetyl derivative of poly[(2,2'-diamino)diphenylene( 1,6-)hexane(5 ,5 l.

12. A composition of matter comprising a product defined in claim 11 dissolved in a solvent therefor.

13. The process for the production of poly-(diaminodiphenylene alkanes) which comprises heating a mixture comprising a polymethylene glycol having from 6 to 18 carbon atoms and a substance selected from the group consisting of 2,2-diarninodiphenyl and 3,3-diaminodiphenyl, and derivatives of said diaminodiphenyls having nuclear substituents selected from the group consisting of alkyl radicals containing from 1 to 3 carbon atoms, aryl radicals of the benzene series, and halogen atoms attached directly to the phenyl rings at any position except the positions para to the amino groups, until a poly- (diaminodiphenylene alkane) is produced having the structure of the compounds (a) and '(b) of claim 1 herein.

14. The process as in claim 13, in which the mixture heated also comprises a dihydrohalide selected from the group consisting of the dihydrochloride and dihydrobromide of the diaminodiphenyl.

15. The process for the production of a poly-(diaminodiphenylene alkane) which comprises heating a mixture of a polymethylene glycol containing 6 to 18 carbon atoms, a metal halide selected from the group consisting of zinc chloride and cobalt chloride, and a substance selected from the group consisting of 2,2-diaminodiphenyl, 3,3'-diaminodiphenyl and derivatives of said diamino- 1. Alinear polymeric substance selected from the group diphenyls having nuclear substituents selected from the consisting of (a) compounds having the general formula group consisting of alkyl radicals containing from 1 to R1 lTlHa NH: Rs Ill; NH: NHi Ilia R R; R -R5 (CH) Ra R4 (CH) R! R4 2 2 L 2 1]" (b) compounds having the general formula 11TH; R1 Iltu NH: NH: 1'11 l u 17H:

Rs 4 R1 4 (CH2); (CH1), 1'

3 carbon atoms, aryl radicals of the benzene series, and halogen atoms attached directly to the phenyl rings at any position except the positions para to the amino groups, until the poly(diaminodiphenylene alkane) is produced having the structure of the compounds (a) and (b) of claim 1 herein, treating the crude reaction product with aqueous alkali metal hydroxide, and separating the poly(diaminodiphenylene alkane) 16. The process of claim 15, in which the mixture heated comprises 2,2-diaminodiphenyl and hexarnethylene glycol.

17. The process of claim 15, in which the mixture heated comprises 2,2'-diaminodiphenyl and decamethylene glycol.

18. The process of claim 15, in which the mixture heated comprises 2,2'-diaminodiphenyl, hexamethylene glycol, zinc chloride and 2,2'-diami11odiphenyl dihydrochloride.

19. The process of claim 15, in which the mixture heated comprises 2,2-diarninodiphenyl, decamethylene glycol, zinc chloride and 2,2-diaminodiphenyl dihydro- 10 chloride.

i No references cited.

. ange 

1. A LINEAR POLYMERIC SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF (A) COMPOUNDS HAVING THE GENERAL FORMULA 